Stannous salt and sodium tripolyphosphate oral care compositions and methods

ABSTRACT

Oral care compositions containing a stannous salt and sodium tripolyphosphate are provided where stannous tripolyphosphate ionic intermediates comprise less than about 1 of the compositions. Tetrasodium pyrophosphate, a methylvinyl ether-maleic anhydride copolymer and/or a silica oral polishing agent may be added for further efficacy. In a single phase blend, the oral care composition may be effectively limited to comprise less than about 10% water. In a dual-phase blend, a mixture having the stannous salt in a first phase and the sodium tripolyphosphate in a second phase may be generated from a dual chamber storage tube (with each phase provided from a separate chamber) prior to dental care usage.

CROSS-REFERENCE TO RELATED APPLICATION

This present application is a continuation of U.S. application Ser. No.13/905,280, filed May 30, 2013, which is a continuation of U.S.application Ser. No. 12/094,817, filed May 23, 2008, now U.S. Pat. No.8,481,004, which is a national stage entry under 35 U.S.C. §371 ofinternational Patent Application No. PCT/US2006/061134, filed Nov. 21,2006, which claims benefit of U.S. Provisional Patent Application No.60/739,130 filed Nov. 23, 2005; the contents of which are herebyincorporated by reference in their entireties.

BACKGROUND OF THE INVENTION

Stannous salts such as stannous fluoride are used in dentifrices asagents for preventing plaque. However, some disadvantages of stannoussalts include instability, tendency to stain teeth, astringency andunpleasant taste for users. For that reason, oral care compositionscontaining stannous salts such as stannous fluoride are often presentedas dual phase compositions, in which the stannous salt is kept separatefrom the other components in order to reduce its negative effects on theoral cavity, such as astringency and unpleasant taste. See, e.g., U.S.Pat. No. 6,521,216 and U.S. Pat. No. 7,063,833, both to Glandorf et al.

Sodium tripolyphosphate is an effective anticalculus (anti-tartar)agent, but the compound is not generally compatible with stannous saltsin long term storage (such as that normally sustained in the lifetime ofa tube of toothpaste between time of packaging and time of discard afteruse), in particular, the combination of sodium tripolyphosphate withstannous salts such as stannous fluoride can lead to undesirablestannous tripolyphosphate intermediates.

Accordingly, there is an ongoing need for oral care compositions thathave improved efficacy in combating plaque and tooth discoloration andare still able to retain long-term stability.

BRIEF SUMMARY OF THE INVENTION

An oral care composition comprising:

(a) about 0.01 to about 5% stannous salt;

(b) about 001 to about 15% sodium tripolyphosphate;

(c) less than about 10% by weight water; and

(d) about 0.1 to about 15% by weight of a methylvinyl ether-maleicanhydride copolymer; wherein the composition comprises less than about1% of stannous tripolyphosphate ionic intermediates.

A dual-phase oral care composition comprising:

(a) a first phase comprising about 0.01 to about 5% stannous salt in afirst orally acceptable vehicle; and

(b) a second phase comprising about o about 15% sodium tripolyphosphatein a second orally acceptable vehicle;

wherein the first phase is in fluid interface with the second phase, andwherein the total water concentration in the oral care composition isless than about 10%.

A method for making an oral care composition, comprising blending: (a)about 0.01 to about 5% stannous salt; (b) about 0.01 to about 15% sodiumtripolyphosphate; and (c) about 0.1 to about 5% of a methyivinylether-maleic anhydride copolymer.

An oral care kit comprising a container containing a mixture of: (a)about 0.01 to about 5% stannous salt; (b) about 0.01 to about 15% sodiumtripolyphosphate; and (c) less than about 10% by weight water; whereinthe comprises less than about 1% stannous tripolyphosphate ionicintermediates.

An oral care kit, comprising:

(a) a first chamber having a first outlet in fluid communication withthe first chamber for discharge of a first dentifrice from the firstchamber; and

(b) a second chamber having a second outlet in fluid communication withthe second chamber for discharge of a second dentifrice from the secondchamber;

wherein the first dentifrice comprises about 0.01 to about 5% stannoussalt in a first orally acceptable vehicle, the second dentifricecomprises about 0.01 to about 15% sodium tripolyphosphate and about 0.1to about 15% of a methylvinyl ether-maleic anhydride copolymer in asecond orally acceptable vehicle, and

-   -   wherein the second outlet is proximate to the first outlet so        that, during simultaneous discharge of the first dentifrice from        the first chamber through the first outlet and of the second        dentifrice from the second chamber through the second outlet,        discharged first dentifrice fluidly interfaces with discharged        second dentifrice to form a mixture in which the discharged        first dentifrice provides at least one first portion of the        mixture and the discharged second dentifrice provides at least        one second portion of the mixture.

A method for cleaning the surface of a tooth comprising the step ofapplying a composition comprising:

(a) about 0.01 to about 5% stannous salt;

(b) about 0.01 to about 15% sodium tripolyphosphate;

(c) less than about 10% by weight water; and

(d) about 0.1 to about 15% by weight of a methylvinyl ether-maleicanhydride copolymer;

wherein the composition comprises less than about 1% stannoustripolyphosphate ionic intermediates, to the surface.

A method for maintaining systemic health of a human or mammal comprisingthe step of applying a composition comprising:

(a) about 0.01 to about 5% stannous sail;

(b) about 0.01 to about 15% sodium tripolyphosphate;

(c) less than about 10% by weight water; and

(d) about 0.1 to about 15% by weight of a methylvinyl ether-maleicanhydride copolymer;

wherein the composition comprises less than about 1%) stannoustripolyphosphate ionic intermediates, to the oral surfaces of the humanor mammal.

DETAILED DESCRIPTION OF THE INVENTION

As used throughout the present disclosure, ranges are a shorthand fordescribing each and every value within the range. Any value within therange can be selected as the terminus of the range. In addition, allreferences cited in the present disclosure are hereby incorporated byreference in their entireties. Where there is any conflict betweendefinitions in the disclosures of the references cited and the presentdisclosure, the present disclosure is controlling.

In certain embodiments, the invention is directed to a dual phasecomposition and oral care kit wherein stannous salt and sodiumtripolyphosphate are formulated to be physically separated in twoseparate aqueous mixtures. Each of the two aqueous mixtures is stored ina physically separate chamber (such as in a dual-compartment tube oftoothpaste), and the two aqueous mixtures are blended together into amixture when the anticipated time between mixture formation andapplication of the mixture to the teeth is sufficiently minimal suchthat the reaction time needed for migration of the stannous ion and thetripolyphosphate ionic complex into an ionic intermediate configurationfir the stannous tripolyphosphate is not sufficient for stannoustripolyphosphate ionic intermediate formation prior to use.

In certain embodiments, at least one of tetrasodium pyrophosphate, amethylvinyl ether-maleic anhydride copolymer or a silica oral polishingagent may be optionally mixed into the formulation. In certainembodiments, the methylvinyl ether-maleic anhydride copolymer has thestructural formula

wherein n is an integer that provides molecular weight in the agent ofabout 60,000 to about 500,000. Examples of suitable methyl vinylether-maleic anhydride copolymers for the present invention arecopolymers of methyl vinyl ether and maleic anhydride available underthe trade name Gantrez® (for example, Gantrez® S-96, Gantrez® S-97,Gantrez® MS and MS-955, Gantrez® ES, ES-225 and ES-425 available fromInternational Specialty Products, Wayne, N.J., USA).

In certain embodiments, the present invention provides compositionscomprising an orally acceptable carrier or vehicle. As used herein, an“orally acceptable carrier” and “orally acceptable vehicle” are usedinterchangeably, and refer to a material or combination of materialsthat is safe for use in the present compositions, commensurate with areasonable benefit/risk ratio, with which the other ingredients may heassociated while retaining significant clinical efficacy. Such carriermaterials should be selected for compatibility with the otheringredients of the compositions, and preferably do not substantiallyreduce the efficacy of the other ingredients. Selection of specificcarrier components is dependent on the desired product firm, includingdentifrices, rinses, gels, and paints.

Materials useful in carriers include but are not limited to: adhesionagents, viscosity modifiers, diluents, surfactants, foam modulators,peroxide activators, peroxide stability agents, abrasives, pH modifyingagents, humectants, mouth feel agents, sweeteners, flavorants,colorants, and combinations thereof As used herein, an “adhesion agent”is a material or combination of materials that enhances the retention ofan ingredient to an oral cavity surface onto which it is applied. Suchadhesion agents include without limitation: adhesives, film formingmaterials and viscosity enhancers; for example, hydrophilic organicpolymers, hydrophobic organic polymers, silicone gums, siliconeadhesives, silicas, and combinations thereof.

In certain embodiments, any of tetrasodium pyrophosphate, a methylvinylether maleic anhydride copolymer, and/or a silica oral polishing agentare independently mixed into the oral care composition. in certainembodiments, the silica oral polishing agent is high cleaning silica. incertain embodiments, the stannous salt comprises a stannous halide suchas stannous fluoride, stannous chloride dehydrate: organic stannouscarboxylate salts such as stannous formate, acetate, gluconate, lactate,tartrate, oxalate, malonate and citrate: stannous ethylene glyoxide, andmixtures thereof. One or more stannous salts are optionally present in atotal amount of about 0.01% to about 5%, optionally about 0.05 to about4%, about 0.1 to about 3%, about 0.5 to about 2% or about 0.1 to about1%.

In certain embodiments, the oral care composition comprises a mixturehaving:

(a) a first phase comprising a first orally acceptable aqueous vehicle;and

(b) a second phase comprising a second orally acceptable aqueousvehicle; where a stannous salt is mixed into the first orally acceptableaqueous vehicle, sodium tripolyphosphate is mixed into the second orallyacceptable aqueous vehicle; and the first phase provides at least onefirst portion of the mixture, the second phase provides at least onesecond portion of the mixture, and at least one of the first portion isin fluid interface with at least one of the second portion in themixture.

In certain embodiments, any of tenasodium pyrophosphate and/or a silicaoral polishing agent (such as high cleaning silica) may be independentlymixed in at least one phase of the first phase and the second phase, incertain embodiments of the mixture, a methylvinyl ether-maleic anhydridecopolymer, such as that of Formula I, is mixed in the second phase.

In certain embodiments, the present invention is directed to methodscomprising:

(a) mixing about 0.01 to about 5% stannous salt into a first orallyacceptable aqueous vehicle to provide a first phase;(b) mixing about 0.01 to about 15% sodium tripolyphosphate into a secondorally acceptable aqueous vehicle to provide a second phase:(c) storing the first phase in a first enclosure,(d) storing the second phase in a second enclosure; and(e) removing the first phase from the first enclosure and removing thesecond phase from the second enclosure so that the first phase and thesecond phase together provide the mixture.

In certain embodiments, the invention further provides a first type oforal care kit as a container containing a mixture of

(a) about 0.01 to about 5% stannous salt; and(b) about 0.01 to about 15% sodium tripolyphosphate;wherein the mixture comprises less than about 1% stannoustripolyphosphate ionic intermediates and comprises less than about 10%water.

In certain embodiments, the invention provides a second type of oralcare kit, comprising:

(a) a first chamber having a first outlet in fluid communication withthe first chamber for discharge of a first dentifrice from the firstchamber; andb) a second chamber having a second outlet in fluid communication withthe second chamber for discharge of a second dentifrice from the secondchamber;wherein the first dentifrice comprises stannous salt in a first orallyacceptable vehicle, the second dentifrice comprises sodiumtripolyphosphate in a second orally acceptable vehicle, and the secondoutlet is proximate to the first outlet so that, during simultaneousdischarge of the first dentifrice from the first chamber through thefirst outlet and of the second dentifrice from the second chamberthrough the second outlet, the discharged first dentifrice interfaceswith discharged second dentifrice to form a mixture.

Thickening agents useful for the present invention include, withoutlimitation: carboxyvinyl polymers, carrageenans (also known as Irishmoss and more particularly iota-carrageenan). cellulosic polymers suchas hydroxyethylcellulose, carboxymethylcellulose (carmellose) and saltsthereof (e.g., carmellose sodium), natural gums such as karaya, xanthan,gum arabic and tragacarith, colloidal magnesium aluminum silicate,colloidal silica, and mixtures thereof.

Viscosity modifiers useful for the present invention include, withoutlimitation: mineral oil, petrolatum, clays and organomodified clays,silica, and mixtures thereof. In various embodiments, the viscositymodifiers are able to inhibit settling or separation of ingredients, orto promote redispersibility upon agitation of a liquid composition.

Diluents useful for the present invention include, without limitation,materials or combinations of materials that can solubilize and/orsuspend other components. In various embodiments, diluents can adjustthe viscosity of the composition, optionally in conjunction withviscosity modifiers as discussed herein and other components of thecomposition.

Surfactants useful for the present invention include, withoutlimitation: anionic, nonionic, and amphoteric surfactants. Surfactantsmay be used, for example, to provide enhanced stability of theformulation, to help in cleaning the oral cavity surfaces throughdetergency, and to provide foam upon agitation, e.g., during brushing.Suitable anionic surfactants include, e.g., water-soluble salts of C₈₋₂₀alkyl sulfates, sulfonated monoglycerides of C₈₋₂₀ fatty acids,sarcosinates, taurates; e.g., sodium lauryl sulfate, sodium coconutmonoglyceride sulfonate, sodium lauryl sarcosinate, sodium laurylisoethionate, sodium laureth carboxylate and sodium dodecylbenzenesulfonate, and mixtures thereof. Suitable nonionic surfactantsinclude, e.g., poloxamers, polyoxyethylene sorbitan esters, fattyalcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides,tertiary phosphine oxides, dialkyl sulfoxides, and mixtures thereof.

Foam modulators useful for the present invention include, withoutlimitation: materials operable to increase amount, thickness orstability of foam generated by the composition (e.g., dentifricecompositions) upon agitation. Any orally acceptable foam modulator canbe used, including polyethylene glycols (PEGs), also known aspolyoxyethylenes. High molecular weight PEGs are suitable, includingthose having an average molecular weight of about 200,000 to about7,000,000, for example about 500,000 to about 5,000,000 or about1,000,000 to about 2500,000. One or more PEGs are optionally present ina total amount of about 0.1% to about 10%, for example about 0.2% toabout 5% or about 0.25% to about 2%.

Humectants useful for the present invention include, without limitation:polyhydric alcohols such as glycerin, sorbitol, xylitol or low molecularweight PEGs. In various embodiments, humectants can prevent hardening ofpaste or gel compositions upon exposure to air. In various embodimentshumectants also function as sweeteners.

In certain embodiments directed to a two-phase oral care compositionhaving a stannous salt in a first phase and sodium tripolyphosphate in asecond phase, the measured pH of the first phase is sustained at about 2to about 8, and the measured pH of the second phase is sustained atabout 5 to about 11. The embodiments, therefore, provide an effectivelyacid pH (a chemical pH of about 7 or less) in the first phase with ameasured pH (the pH measured when a probe is inserted into the phase) ofbetween about 2 and about 8 and an effectively alkaline pH (a chemicalpH of between about 7 and about 11) in the second phase with a measuredpH (again, the pH measured when a pH probe is inserted into the phase)of between about 5 and about 11.

Any other desired components may be added to the compositions,including, for example, mouth-feel agents, pH modifying agents,flavorants, sweeteners, additional anticalculus and antiplaque agents,abrasives, polishing agents, antimicrobial (e.g., antibacterial) agentssuch as those described in U.S. Pat. No. 5,776,435, saliva stimulants,anti-inflammatory agents, H₂ antagonists, nutrients, vitamins, proteins,antioxidants, colorants, or additional active materials useful for theprevention or treatment of a condition or disorder of hard or softtissue of the oral cavity, the prevention or treatment of aphysiological disorder or condition, or to provide a cosmetic benefit.

Certain embodiments provide oral care compositions having stannous saltand sodium tripolyphosphate in a first phase comprising a first orallyacceptable aqueous vehicle and in a second phase comprising a secondorally acceptable aqueous vehicle. The first and second phases may beindependently formulated such that the stannous salt is mixed into thefirst orally acceptable aqueous vehicle and such that the sodiumtripolyphosphate is mixed into the second orally acceptable aqueousvehicle. The first phase may be maintained at a measured pH of about 2to about 8, and the second phase may be maintained at a measured ofabout 5 to about 11. The first and second phases may be kept fromphysical chemical interaction prior to a brief period prior toapplication to a tooth surface. At that time, the first and secondphases may be combined together (e.g., on a toothbrush) as a mixture (acombination of different components) where the first phase provides atleast one first portion of the mixture, the second phase provides atleast one second portion of the mixture, and the at least one firstportion is in fluid interface with the at least one second portion inthe mixture. This may be achieved by, for example, use of adual-compartment toothpaste tube where two approximately equivalentvolumetric portions from each of the two compartments are simultaneouslyextruded onto a toothbrush under the presumption that the resultingmixture dentifrice is to be immediately applied to the teeth by theuser.

In certain embodiments, a two-phase mixture provides an oral carecomposition having stannous fluoride as the stannous salt and sodiumtripolyphosphate in differentiated phases where the first phase is mixedto compose a measured pH of about 2 to about 8. In various embodiments,this first phase and the second phase each may additionally comprise oneor more ingredients chosen from citric acid, trisodium citrate &hydrate,an additional stannous salt, glycerine, a cellulosic polymer such as,e.g., sodium carboxymethyl cellulose (Sodium CMC 2000), a gum such asxanthan gum or carrageenan gum (e.g., iota carrageenan), a flavorant(such as. e.g., the sweeteners sodium saccharin or sorbitol) anadditional sail such as, e.g. tetrasodium pyrophosphate, polymer suchas, e.g., polyoxypropylene-polyoxyethylene block polymer (PLURONIC®F127), titanium dioxide, an oil such as, e.g., castor oil, silicondioxide, precipitated silica, synthetic amorphous silica, or sodiumlauryl sulfate.

In various embodiments, the compositions comprise, further to the firstphase described in (a) above, a second phase (b) which is mixed tocomprise a measured pH about 5 to about 11.

The compositions of the present invention optionally comprise silicaoral polishing agent (“silica abrasive”) in at least one of the phases.In various embodiments, silica may be mixed at, for example, about 10 toabout 50%, about 15 to about 40% or about 20 to about 30% dental typeprecipitated amorphous hydrated silicon dioxide; and at about 10 toabout 15%, about 11 to about 14 and about 12 to about 13% syntheticamorphous silica.

In the dual phase mixture embodiments having at least two portions whereeach is extruded from an independently stored phase, silica may beprovided in the first phase as about 10 to about 50% dental typeprecipitated amorphous hydrated silicon dioxide, less than about 8%synthetic amorphous precipitated silica, less than about 15% syntheticamorphous silica, in the second phase, in various embodiments silica maybe provided in an amount of about 10 to about 50% precipitated syntheticamorphous silica, less than about 15% synthetic amorphous silica, orless than about 8% synthetic amorphous precipitated silica.

In various embodiments, the compositions comprise silica in the form ofsilica gel, hydrated silica or precipitated silica, alumina, insolublephosphates, calcium carbonate, resinous abrasives such asurea-formaldehyde condensation products, and mixtures thereof, insolublephosphates useful as abrasives include, for example, orthophosphates,polymetaphosphates and pyrophosphates; e.g., dicalcium orthophosphatedihydrate, calcium pyrophosphate, dicalcium pyrophosphate, tricalciumphosphate, calcium polymetaphosphate and insoluble sodiumpolymetaphosphate or mixtures thereof. One or more abrasives areoptionally present in an abrasive effective total amount of, in variousembodiments, about 5% to about 70%, about 10% to about 50%, or about 15%to about 30% by weight of the composition. Average particle site of anabrasive, if present, is generally about 0.1 to about 30 microns, forexample about 1 to about 20 microns or about 5 to about 15 microns. Theuse of silica as previously noted is preferred to reduce staining of theteeth due to the stannous fluoride.

In various embodiments, the present methods include adding and mixingthe ingredients in a suitable vessel such as a stainless steel tankprovided with a mixer. In certain embodiments, the stannous salt ismixed into a first orally acceptable aqueous vehicle to provide a firstphase of a dentifrice; the sodium tripolyphosphate is mixed into asecond orally acceptable aqueous vehicle to provide a second phase ofthe dentifrice; the first phase is stored in a first enclosure; thesecond phase is stored in a second enclosure; and the first phase isexpelled from the first enclosure and the second phase is expelled fromthe second enclosure just prior to application to the teeth so that thefirst phase and the second phase together provide a mixture. In variousembodiments, the resultant mixture has at least one first portioncomprising the first phase, the mixture has at least one the secondportion comprising the second phase, and each first portion is in fluidinterface with at least one second portion.

In various embodiments, the mixture may be provided to the consumer inthe form of an oral care kit providing (a) a first chamber (the firststorage enclosure for storing, the first phase of the mixture) having afirst outlet in fluid communication with the first chamber for dischargeof a first dentifrice from the first chamber; and (b) a second chamber(the second storage. enclosure for storing the second phase of themixture) having a second outlet in fluid communication with the secondchamber for discharge of a second dentifrice from the second chamber. Invarious embodiments, the second outlet is proximate to the first outletso that, during simultaneous discharge of the first dentifrice from thefirst chamber through the first outlet and of the second dentifrice fromthe second chamber through the second outlet, discharged firstdentifrice fluidly interfaces with discharged second dentifrice to formthe mixture. In certain embodiments, equal amounts of each phase aredelivered into the mixture so that the consumer has a convenient basisfor ascertaining that both phases are being delivered and that rapidintermixing of the phases will occur as the mixture is brushed againstthe teeth.

Additional ingredients such as flavorant, coloring or sweeteners areadded at any point during the mixing process but in various embodimentssuch ingredients are preferably added last or close to last.

The present invention also provides methods for treating a tooth surfaceusing compositions according to the present invention. In certainembodiments, the methods comprise applying a composition of the presentinvention to the tooth surface. As referred to herein, “applying” refersto any method by which a compositional embodiment is placed in contactwith the tooth surface. Such methods, in various embodiments, comprisedirect application of a composition by such methods as painting andbrushing. Suitable application devices include, e.g., toothbrushes.

In one prophetic example, a composition according to the presentinvention comprises less than about 10% water, and further comprises:

about 0.4 to about 0.8% stannous salt,

about 0.20 to about 24% polyhydric alcohol,

about 10.0 to about 17% amorphous silica,

about 0.5 to about 4% tetrasodium pyrophosphate; and

about 1 to about 15% sodium tripolyphosphate.

In another prophetic example, a composition according to the presentinvention comprises:

about 0.4 to about 0.8% stannous salt,

about to about 9% water,

about 0.2 to about 24% polyhydric alcohol,

about 0.5 to about 4% tetrasodium pyrophosphate,

about 1 to about 15% sodium tripolyphosphate, about 10 to about 50%dental type precipitated amorphous hydrated silicon dioxide; and

about 10 to about 17% amorphous silica.

In one prophetic example, the composition comprises stannous fluoride asthe stannous salt, and

(i) the first phase is mixed to comprise:

about 0.9 to about 1.8% stannous fluoride,

about 0.3 to about 1% stannous chloride dihydrate,

about 0.5 to about 4% tetrasodium pyrophosphate,

about 10 to about 50% precipitated amorphous hydrated silicon dioxide,

less than about 8% synthetic amorphous precipitated silica,

less than 15% synthetic amorphous silica; and

(ii) the second phase is mixed to comprise:

about 0.5 to about 4% tetrasodium pyrophosphate,

about 0.1 to about 15% methylvinyl ether-maleic anhydride copolymer,

about 1 to about 15% sodium tripolyphosphate,

about 10 to about 50% precipitated synthetic amorphous silica, and

less than about 15% synthetic amorphous silica.

By way of further example, and not limitation, specific embodiments ofthe present invention are illustrated in the following Examples.

EXAMPLE 1

A dual component composition of the present invention may be prepared byindependently combining the ingredients of “Side 1” and “Side 2” ofTable I:

TABLE I Side 1 Weight %) (Stannous Portion) q.s. Purified Water 0.01-2 Citric Acid Anhydrous 0.5-5 Trisodium Citrate Dihydrate 0.2-1 StannousFluoride 0.2-2 Stannous Chloride Dihydrate   20-40 Glycerin 0.1-5 SodiumCarboxymethyl Cellulose  0.1-10 Xanthan Gum 0.1-5 Sodium Saccharin 0.1-5Tetrasodium Pyrophosphate  0.5-10 Pluronic F127 Polyoxypropylene -Polyoxyethylene Block Polymer 0.1-5 Titanium Dioxide  0.5-20 Oil   1-15Dental Type Precipitated Amorphous Hydrated Silicon Dioxide   1-10Synthetic Amorphous Precipitated Silica   1-15 Synthetic AmorphousSilica   1-15 Sodium lauryl sulfate 30% Solution 0.01-10 Flavor Side 2(Tartar Control Portion) q.s. Purified Water 0.1-1 Sodium Saccharin  5-60 Sorbitol 0.01-5  Tetrasodium Pyrophosphate   1-15 Gantrez S-9713% Liquid 0.5-5 Sodium Hydroxide 50% 0.01-5  Titanium Dioxide   1-20Glycerine   1-15 Sodium Tripolyphosphate 0.01-5  Sodium CMC 2000S-12Sodium Carboxymethyl Cellulose  0.1-10 Iota Carrageenan   1-30Precipitated Synthetic Amorphous Silica   1-20 Synthetic AmorphousSilica   1-10 Sodium lauryl sulfate 0.01-10 Flavor

We claim:
 1. An oral care composition comprising: (a) about 0.01 toabout 5% stannous salt; (b) about 0.01 to about 15% sodiumtripolyphosphate; (c) 10% or less water; and (d) about 0.1 to about 15%of a methylvinyl ether-maleic anhydride copolymer; wherein thecomposition comprises less than 1% stannous tripolyphosphate ionicintermediates, wherein (a), (b), (c) and (d) are blended together; andoptionally further comprises an agent selected from the group consistingof adhesion agents. anticalculus agents, antiplaque agents,antimicrobial agents, viscosity modifiers, diluents, surfactants, foammodulators, peroxide activators, peroxide stability agents, abrasives,pH modifying agents, humectants, mouth feel agents, sweeteners,flavorants, colorants, and combinations thereof.
 2. The composition ofclaim 1, comprising about 0.1 to about 3% stannous salt.
 3. Thecomposition of claim 1, comprising about 0.1 to about 10% sodiumtripolyphosphate.
 4. The oral care composition of claim 1 wherein thestannous salt is stannous fluoride.
 5. The composition of claim 1,comprising less than 8% water.
 6. The composition of claim 1, comprisingless than 6% water.
 7. The composition of claim 1 further comprising acompound chosen from tetrasodium pyrophosphate and a silica polishingagent.
 8. The composition of claim 1 wherein the methylvinylether-maleic anhydride copolymer is represented by formula (1):

wherein n is an integer that provides a molecular weight of saidcopolymer of about 60,000 to about 500,000.
 9. An oral care kitcomprising a container containing a mixture of (a) about 0.01 to about5% stannous salt:, (b) about 0.01 to about 15% sodium tripolyphosphate;(c) 10% or less by weight water; and (d) an orally acceptable carrierselected from the group consisting of adhesion agents, viscositymodifiers, diluents, surfactants, foam modulators, peroxide activators,peroxide stability agents, abrasives, pH modifying agents, humectants,mouth feel agents, sweeteners, flavorants, colorants, and combinationsthereof; wherein the mixture comprises less than about 1% stannoustripolyphosphate ionic intermediates.
 10. The oral care kit of claim 9wherein the mixture comprises less than 8% water.
 11. The oral care kitof claim 9 wherein the mixture further comprises tetrasodiumpyrophosphate.
 12. The oral care composition of claim 2, comprisingabout 0.1 to about 10% sodium tripolyphosphate and less than 8% water.13. The oral care composition of claim 12, wherein the stannous salt isstannous fluoride.
 14. The composition of claim 13 wherein themethylvinyl ether-maleic anhydride copolymer is represented by formula(I):


15. The oral care composition of claim 14 further comprising a compoundchosen from tetrasodium pyrophosphate and a silica polishing agent. 16.The oral care composition of claim 1, wherein the adhesion agents areselected from the group consisting of adhesives, film forming materialsand viscosity enhancers, hydrophilic organic polymers, hydrophobicorganic polymers, silicone gums, silicone adhesives, silicas, andcombinations thereof.
 17. The oral care composition of claim 1, whereinthe stannous salt is selected from the group consisting of stannoushalide, stannous fluoride, stannous chloride dehydrate; organic stannouscarboxylate salts such as stannous formate, acetate, gluconate, lactate,tartrate, oxalate, malonate and citrate; stannous ethylene glyoxide, andmixtures thereof.
 18. The oral care composition of claim 1 wherein theabrasive is selected from the group consisting of silica gel, hydratedsilica, precipitated silica, alumina, insoluble phosphates, calciumcarbonate, resinous abrasives, urea-formaldehyde condensation products,orthophosphates, polymetaphosphates and pyrophosphates, dicalciumorthophosphate dihydrate, calcium pyrophosphate, dicalciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate andinsoluble sodium polymetaphosphate and mixtures thereof.